Process for the preparation of novel hydrocarbon resins

ABSTRACT

A process for the preparation of novel hydrocarbon resins having excellent thermal stability and low melt viscosity which comprises polymerizing a mixture mainly of 1,3-pentadiene, cyclopentene and diisobutylene in the presence of Friedel-Crafts type acidic metal halide catalyst.

United States Patent litiornai et a1,

,iiii a, 1975 PROCESS FOR THE PREPARATKUN 0F NOW/EL HYDRUCARBON RESTNSinventors: Hisatalka Komai; Atsoo Ishikawa;

Hidemi Tsubaki, all of Kawasaki,

Japan Assignee: Nippon Zeon Co. lLtd., Tokyo, Japan Filed: Oct. 5, 11973Appl. No.: 404,023

Foreign Application Priority Data Oct. 12, 1972 Japan 47l02l54 Cl.260/80.7; 260/5; 260/27 BB; 260/28.5 B; 260/33.6 UA; 260/33.8 UA;260/82; 260/878 R lint. C11. 1. (108i 11/72 Field of Search 260/80.7, 82

[56] References Cited UNlTEl) STATES PATENTS 2,963,467 12/1960 Small260/82 3,005,806 10/1961 Fefer 260/82 Primary ExaminerStanford M. LevinAttorney, Agent, or Firm-Bucknam and Archer [57] ABSTRAQT 7 Claims, NoDrawings PLRQCESS FUR Tllilli PREPARATION O l NOVEL HYDRQQATUTGNRlESllNS This invention relates to a process for the preparation or" anovel hydrocarbon resin and more particularly it relates to a processfor the preparation of an industrially useful hydrocarbon resin bypolymerizing a monomeric mixture mainly of 1,3-pentadiene, cyclopenteneand diisobutylene in the presence of an acidic metal halide.

It has heretofore been known that the cationic polymerization of1,3-pentadiene gives polymers exhibiting various different properties.These polymers may be in the form of liquid, gel or the like and wasemployable for specific uses depending on their specific properties.However, they were not found valuable in the industrial field in whichrosin and its derivatives, terpene resin or the like has been used.There have recently been made various attempts to produce improvedpolymers of 1,3- pentadiene with the result of development of suchprocesses as follows:

A process for copolymerizing 1,3-pentadiene and 2- methyl-Z-butene(Japanese Pat. Gazette No. 12306/70), and

A process for copolymerizing 1,3-pentadiene, 1,3- butadiene,2-rnethyl-l-butene and 2-methyl-2-butene (Japanese Pat. Gazette No.1991/72).

Resinous polymers obtained by polymerizing 1,3- pentadiene by the use ofthese recently developed processes have come to be paid attention to asan industrially useful material which may be substituted for rosin orterpene resins.

It has been found by the present inventors that, in the course of theirstudies on cationic polymerization of 1,3-pentadiene, excellenthydrocarbon resins may be produced by the copolymerization of1,3-pentadiene and cyclopentene. These resinous polymers were equivalentor superior to the conventionally used aliphatic petroleum resins inwater repellency, adhesion, cohesive strength, peel strength, thermalstability and the like, while they are somewhat disadvantageous incompatibility with polyethylene, ethylenevinyl acetate copolymers,paraffin wax or the like and are troublesome to handle due to their highviscosity in their molten state. Thus, they still have not a fewdrawbacks to be overcome and have therefore been desired to be improved.

As a result of their studies made in an attempt to eliminate theaforesaid drawbacks by copolymerizing a third comonomer with1,3-pentadiene and cyclopentene, the present inventors have found thatthe copolymerization of diisobutylene as the third comonomer with1,3-pentadiene and cyclopentene gives excellent hydrocarbon resins, thusaccomplishing this invention.

An object of this invention is to provide polymers which have a low meltviscosity and are excellent in thermal stability and in compatibilityallowing the polymer and a paraffin wax, polyethylene, ethylenevinylacetate or the like to be dissolved in each other.

This object is achieved by polymerizing a monomeric mixture comprising35 85 percent by weight of 1,3- pentadiene, l 50 percent by weight ofdiisobutylene and 5 30 percent by weight of cyclopentene or polymerizinga mixture comprising not less than 80 parts by weight of said monomericmixture and not more than parts by weight of at least one otherunsaturated hydrocarbon copolymerizable with said monomeric mixture, inthe presence of a Friedel-Crafts type acidic metal halide catalyst.

Friedel-Crafts type acidic metal halides typically include thefluorides, chlorides, bromides and iodides of metals such as aluminum,boron and iron. lnter alia, aluminum halides such as aluminum chlorideand bromide, and boron trifluoride are particularly preferable. The useof boron trifluorideetherate, an alkylaluminum dihalide or the likewhich is liquid at ambient temperature, will produce a liquid polymer.Titanium tetrachloride is remarkably low in polymerizing activity as aFriedel-Crafts type catalyst. Most preferably, aluminum chloride isused.

ln view of the fact that the contact of the monomeric mixture with thecatalyst is important in the practice of polymerization reactionaccording to this invention, the catalyst may be used in the form ofparticles having a mesh size of usually 5 200, preferably 20 200.However, these mesh sizes are not limitative, and larger and smallerparticles may also be used. Although the amounts of catalyst used arenot particularly limiting, the catalyst is necessary to use in amountsenough to allow the polymerization reaction to take place. The amountsare usually in the range of from 0.1 to 5 percent, preferably from 0.5to 2 percent, by weight of the total monomers. The catalyst may beincorporated in the monomeric mixture, and vice versa; where desired,both of them may concurrently be introduced to a reactor. Thepolymerization reaction, whether effected in a batch or continuousfashion, is carried out in the known manner.

The temperature of polymerization reaction may advantageously becontrolled in the presence of a diluent since the reaction is usually anexothermic one. The diluents which may be used should be inert to thereaction and typically include aromatic hydrocarbons such as benzene,toluene, xylene and monochlorobenzene; aliphatic hydrocarbons such aspentane, hexane and heptane; and alicyclic hydrocarbons such ascyclohexane. However, the use of the aliphatic hydrocarbons as thediluent in the reaction of the monomeric mixture wherein 1,3-pentadieneis contained in a high concentration, will often give a gel-like polymerinconveniently. In order to avoid such inconvenience it is preferable touse a solvent containing aromatic hydrocarbons in amounts of at least 50percent by weight thereof as the diluent. The solvents are used usuallyin amounts of 20 1000 parts by weight per 100 parts by weight of themonomeric mixture.

The monomeric mixture according to this invention comprises 35 percentby weight of 1,3-pentadiene, 5 30 percent by weight of cyclopentene and10 50 percent by weight of diisobutylene. Diisobutylene is ob tained bydimerizing isobutylene contained in a C fraction or isobutylene producedas a by-product in the preparation of sec.-butyl alcohol, and thediisobutylene so obtained is composed mainly of 2,4,4-trimethylpentene-land 2,4,4-trimethylpentene-2. The use of a monomeric mixture comprisingmore than 50 percent by weight of diisobutylene or more than 30 percentby weight of cyclopentene and, in addition, less than 35 percent byweight of 1,3-pentadiene, will lower the monomeric mixture inpolymerizing activity and produce a polymer having a low softeningpoint. Furthermore, the use of a monomeric mixture comprising more than85 percent by weight of 1,3-pentadiene will make unstable apolymerization system in which this mixture is {used or will produce agel-like polymer from the systemf. The diisobutylene contained in themonomeric mixture according to this invention is the most importantconstituent of this invention, andthe object of this invention cannot beattained without diisobutylen e being contained in the .monomericmixture used.

The monomeric mixture according to this invention I,

may contain up to 20 percent, preferably up to percent, by weight ofother copolymerizable unsaturated hydrocarbons in additionto1,3-pentadiene, cyclopentene and diisobutyleneQTypical of saidcopolymerizable hydrocarbons are aliphatic mono; and diolefins having 4to 6 carbon atomssuch as but ene, pentene, hexene, butadiene andisoprene; cyclic olefins such as cyclopentadiene and 'methylcyclop entadiene; and terpenes such as a-pinene, B-pinene and dipentene.

The polymerization reaction is effected at temperathereby obtaining adesired polymer.

The polymers obtained according to i'this invention have a Gardner colorof not higher than 6 as determined from ASTM D- l544-63T, a softeningpoint of 40 160C as prescribed in JIS (Japanese Industrial Standard)K-253 l and a specific gravityof 0.95 1.00. They are resinous polymerswhich are, soluble in aliphatic, aromatic and halogenated hydrocarbonsolvents such as pentane, hexane, benzene, xylene and v chloroform, aswell as in carbon tetrachloride. The resinous polymers of this inventionallow natural and vari oussynthetic rubbers, synthetic resins such aspolyethylene and ethylene-vinyl acetate copolymers, natural resins suchas polyterpenes and rosin, and various waxes, to dissolve in each other.

The resinous polymers according to this invention may be incorporatedespecially in natural and various synthetic rubbers to provide theserubbers with excellent properties such as water repellency,adhesiveness, cohesive strength, peel strength, thermal stability. Theblends soj prepared areusefulas an adhesive for adhesive tapes. Thepolymers are particularly remarkably effective in providing rubbers withadhesiveness when added to the rubbers. The polymers and thermoplastics(such as polyethylene and ethylene-vinyl acetate copolymer which haverecently been used mainly for hot melt adhesives and coating materials)are excellently compatible with each other, and the polymers and paraffin or microcrystalline waxes are also excellently solpounded withsaid thermoplastics or waxes to obtain a composition for use as anadhesive or coating material, they allow the composition to be formedhomogeneous and provided with adhesiveness effectively. The compositionso formed may advantageously be used without being exposed to hightemperatures owing to its low cloud point. Furthermore, the polymersaccording to this invention are effective in providing compositionscontaining them with easy fluidization when applied or coated because oftheir low melt viscosity. These aduble in each other. Thus, in caseswhere they are com- I vantageous features of this invention make itpossible to avoid troubles heretofore caused by the use of theconventional hot melt type adhesive composition, which troubles areillustrated by various loses incurred by heating at high temperatures,that is, supply of large amount of heat; decomposition of adhesivecompositions and bodies to be coated therewith, caused by thermalhysteresis; and change in melt viscosity and evolution of odor broughtabout by said decomposition. In addition, the specific excellent thermalstability of the resinous materials according to this invention allowscompositions containing them to. be stabilized in quality and preventedfrom aging by. the use of less amounts of an anti-aging agent, therebyobtaining economical benefits. I

This invention will be illustrated by the following Examples in whichall the parts are by weight unless otherwise specified.

EXAMPLES 1 3 To a 3-liter glass flask were added g of particulatealuminum chloride of not larger than} a 40-mesh size and 1050 g of amixed solvent containing toluene and isooctane in the ratio by weight of20 to form a mixture which was agitated while being kept at atemperature lower than the predetermined one by 10C. The mixture soobtained was slowly incorporated with 810 g of a mixture of hydrocarbonscontinuously over a time period of 60 minutes to form a polymerizingsystem. To prevent the system from being raised in temperature due tothe exothermic reaction taking place therein, the system was maintained{at the predetermined temperature while being cooled. After thecompletion of the incorporation of the mixture of hydrocarbons, thepolymerizing system was further kept at the predetermined temperaturewhile agitating it for 60 minutes and was then incorporated with 35 mlof a mixture containing methanol and a 28 percent ammonia water in theratio by volume of l 1 thereby to decompose the aluminum chloride. Theparticles produced by the decomposition in the reaction mixture werefiltered out to obtain a filtrate which was transferred into a 3- literglass flask. The flask so charged was heated under a stream of nitrogento distil off the unreacted hydrocarbons and solvent and then raised to230C. To remove the low polymers produced by the reaction and stillremaining solvent from the filtrate, saturated steam continued to beblown into the filtrate until hardly any oily layer was found in thedistillate and then ceased to be blown. The molten residue was withdrawnfrom the flask onto an aluminum tray and allowed to stand for cooling atroom temperature thereby obtaining a resinous material. In addition,none of gel-like materials was found in the inactivated catalystseparated by said filtration. The results are shown in Table l.

The mixture of hydrocarbons used was as follows.

Ingredient Part 1,3-pentadiene 62.9 69.4 Diisobutylene 13.6 15.6Cyclopentene 14. 1 15.0 Saturated hydrocarbons 4.9

, having 5-6carbon atoms Unsaturated hydrocarbons 4.5 having 5-6'carbonatoms Total 100.0 100.0

Table 1 *2 *3 *4 Example Reaction Yield Yield Amount of SofteningGardner Melt temp. rate low polymers point color viscosity (C) (2) 4)(2) (C) (cps) *1 Yield rate is a ratio between the weight of a resin(excluding low polymers) produced and the total weight of1.3-pentudiene. diisobutylcnc and cyclopentcne contained in a mixture ofhydrocarbons used.

2 Determined by the ring and ball method prescribed in HS K-253 l. 3Gardner color as prescribed in ASTM Dl544-63T. '4 Determined at 200C byu Brookl'icld \iscosimcter.

From Table 1 it is seen that with the increase in reaction temperatureused there will be produced resinous products having a higher softeningpoint and somewhat From Table 2 it is apparent that the addition ofdiisobutylene as one of the components of the mixed hydrocarbons willgive resinous products having remarkably higher Gardner color and meltviscosity. In this case, low melt viscosity. however, the resinousproducts are still light in color and still low in melt viscosity ascompared with those containing no diisobutylene.

EXAMPLES 4 7 EXAMPLES 8 9 A 3-liter glass flask was charged with 7.6 gof particulate aluminum chloride of not larger than a 40-mesh size and880 g of a mixed solvent containing benzene and toluene in the ratio byweight of 80 to form a A 511ter glass flask was Charged With g Oparticmixture which was heated and kept at 40C under agi- 1.11316aluminum ChlOI'lClG Of a 4-O-mesh size Of finer and tation. The mixturewas slowly incorporated with 700 1670 g Of a mixed Solvent Containingbenzene and tolug of mixed hydrocarbons continuously over a period oferle In the ratlO y ight f 80 i 20 to form a mixture i f 120 minutes, di hi h th lti l which was kept at approximately 50C under agitation.merizing system was kept at 45C while being cooled to The mixture as sowly incorporated with 1476 g of a avoid undue heating by its exothermicreaction. After mlXtuYe of hydrocarbons contimlQusly Over a Period ofthe end of the incorporation the system was succestlme of 120 mlnutesWhile keeping the Whole mass at sively kept at the same temperature asabove under agitbfl Predetermlrled p rat re by Cooling the mass to whfor 30 mi d th incorpgrated with 30 1 inhibit a raise in temperatureotherwise caused by the of a mixture composed of methanol and a 28percent exothermic reaction therein. After the end ofthe incorammoniawater i th ti b volume f 1 1 d poration the mass was successively keptat the same compose the aluminum chloride' The reaction mixturetemperature as above under agitation for 30 minutes so produced wasfiltered to remove therefrom the inacand incorpo ated ith .75 ml of amixture containing i d Catalyst particles d d b th d i methanol and a 28percent ammonia water in the ratio tion and obtain a filtrate which wastransferred into a 40 by olum Ofl 1, thereby decomposing the aluminum3-liter glass flask wherein the filtrate was then treated Ch ride- Thereaction mixture so produced was filin the same manner as in Example 1to obtain a yellowtered to remove therefrom the inactivated particulatecolored resinous material without production of gelcatalyst produced bysaid decomposition while obtainlike materials in any one of the treatingsteps. The reing a filtrate which was then treated in accordance withgultg are i di d i T bl 2, the procedure of Example 1 thereby to obtaina yellow- The mixtures of hydrocarbons used had the following coloredresinous material without production of gelcompositions. like materialsnoticed.

Mixture A B C D ingredient Part Part Part Part i. oentadiene 59.3 65.451.8 57.2 44.4 49.0 37.0 40.8 ooutylenc 18.1 20.0 27.2 30.0 36.2 40.045.3 50.0 'clopentcne 13.2 14.6 11.6 12.8 10.0 11.0 8.3 9.2

rated hydrocarbons 4.9 4.9 4.9 I 4.9

5-6 carbon atoms llCLl hydrocarbons 4.5 4.5 4.5 4.5 5-6 carbon atomsTable 2 Melt Yield Amount of Softening Gardner viscosity [vii :tureYield rate low polymers point color at 200C (g) (g) (cps) The samecomposition 4 as in 5"" 86.8 25.1 105.5 3 355 Examples 1 3 A 533 84.430.4 101.0 3 320 6 B 490 77.5 35.8 93.5 4 165 f 463 73.3 36.6 89.5 4 1153 453 7:5 42.5 82.0 4

The mixtures of hydrocarbons used had the following compositions. t

this inventionr will give a resinous material having a remarkably highmelt viscosity.

E F Part Part 1,3-pentadiene 59.3 65.4 i 55.5 61.3 Diisobutylene 13.615.0 18.1 20.0 Cyclopentene 13.2 14.6 12.4 13.7 lsoprene 4.5 5.0 4.5 5.0Saturated hydrocarbons 4.9 5.0 having -6 carbon atoms Unsaturatedhydrocarbons 4.5 4.5 having 5-6 carbon atoms Table 3 Melt ExampleMixture Reaction Yield Yield Amount of Softening Gardner viscosity temp.rate low polymers point color at 200C (5) (cps) 9 r E 45 980 91.0 60.8101.0 3 270 10. F 55 940 70.0 77.7 97.0 3 255 r COMPARATIVE EXAMPLE 1 A3-liter glass flask was charged with 7.8 g of particulate aluminumchloride of a 40-mesh size or finer and 930 g of a mixed solventcomprising toluene and isooctane in the ratio by weight of 80 to form amixture which was kept at C under agitation. The mixture so formed wasslowly incorporated with 664 g of a mixture of hydrocarbons continuouslyover a period of time of 60 minutes to prepare a polymerizing systemwhich was kept at C while cooling it to cancel the heat evolved by theexothermic reaction thereof. After the completion of the incorporationthe polymerizing system was successively kept at 50C for 30 minutes andincorporated with'30 ml of a mixture containing methanol and a 28percent ammonia water in the ratio by volume of l: 1 thereby todecompose the aluminum chloride. The reaction mixture so produced wasfiltered to remove therefrom the inactivated catalyst particles whileobtaining a filtrate. The filtrate was transferred into a 3- literglassflask and then treated in the same manner as in Example 1 therebyobtaining 513 g of a resinous material in a yield of 77.3 percent. Thelow polymers recovered amounted to 6.2 g. The resinous material soobtained had a Gardner color of 3, softening point of 890C and meltviscosity of 351 centipoise at 200C. There were found no gel-likematerials produced.

The mixture of hydrocarbons used had the following composition.

From the aforesaid results it is seen that the use of diisobutylene inamounts smaller than those according to COMPARATIVE EXAMPLE 2 To a3-liter glass flask were added 880 g of benzene and 7.6 g of particulatealuminum chloride of a 40- 'mesh size or finer to form a mixture whichwas kept at 25C under agitation. The mixture was slowly incorporatedwith 690 g of a mixture of hydrocarbons continuously over a period oftime of minutes while cooling so that the resulting polymerizing systemwas kept at a reaction temperature of 30C. Ten minutes after the end ofsaid incorporation, the system produced gel-like materials and increasedin viscosity. After further agitated for 20 minutes, the system wasincorporated with 30 ml of a mixture composed of methanol and a 28percent ammonia water in the ratio by volume of l 1 thereby decomposingthe aluminum chloride. The system was filtered to remove the inactivatedcatalyst particles and gel-like materials (the thus-removed massweighing 261 g) while obtaining a filtrate. The filtrate was introducedto a 3-liter glass flask, heated under a stream of nitrogen to distilthe unreacted hydrocarbons and solvent and then raised to 200C under astream of nitrogen for 4 hours to distil off the low polymers producedby the polymerization. The molten residue so obtained was transferredonto an aluminum tray and then let to cool to room temperature therebyobtaining 400 g of a yellow-colored resinous material in a yield of 61.0percentQThis resin had a Gardner color of 4, softening point of 820C andmelt viscosity of 330 centipoise at 250C.

The mixture of hydrocarbons mentioned above had the followingcomposition.

From theresults of the Comparative Example 2, it is seen that the useof-more than percent by weight of 1,3-pentadiene and less than 10percent by weight of diisobutylen'ewill render unstable a polymerizingsystern wherein these monomers are used, thereby producing gel-likepolymers.

Experiment 1 The hydrocarbon resins obtained in Examples 5, 7 andComparative Example 2, as well as terpene resins.

and rosin derivatives were tested for their thermal stability with theresult being indicated in Table 4. It is to be noted that the resinsobtained in said Examples and Comparative Example were not incorporatedwith an antioxidant.

Table 5 indicates the following:

The hydrocarbon resins according to this invention when used in thepreparation of a composition, will permit the resulting composition tokeep its melt viscosity at a low level owing to their intrinsic low meltTable 4 Softening point Gardner color Degree of after heating afterheating ethylenic Softening to 180C for Gardner to 180C for unsaturationpoint 24 hours color 24 hours ExampleS 53 101.0 101.0 3 11 Example 7 3.389.5 890 4 ll Comparative 8.5 89.0 98.5 4 13 Example 1 Piccolyte 3 6114.0 100.0 3 12 S-1 15 Ester gum H 78.5 82.0 6 13 "Ratio between numberof hydrogen atoms related to double bonds and number of the total ofhydrogen atoms in hydrocarbon resin. the ratio being determined bynuclear magnetic resonance spectrometry.

'Terpene resin. produced by Pensylvania Industrial Chemical Corp.Glycerine ester of hydrogenated rosin.

Table Melt viscosity Transparency in Hydrocarbon resin at 170C themolten state Flexibility at Cloud point (cps) at 170C room temperature(C) Example 1 455 Excellent Very good 116 Example 2 380 Very good 128Example 3 430 Excellent Excellent 116 Example 4 450 Very good Very good150 Example 5 350 Excellent 130 Example 6 320 Excellent 91 Example 7 31072 Example 8 310 63 Example 9 430 115 Example 10 430 94 ComparativeExample 1 560 Good Good 170 Comparative Example 2 680 Good Good 170Piccolyte S-1 455 Excellent Excellent 107 Ethylene vinyl 68 acetatecopolymer/ paraffin wax 1/1 As is seen from Table 4, the hydrocarbonresins according to this invention are superior in thermal stabilityand, surprisingly, they hardly change in softening point in spite ofusing no antioxidant therein.

Experiment 2 tent of vinyl acetate: 28%; Melt index: 400 g/10 min. (asdetermined from ASTM D-l238-70) Paraffin wax SP (produced by NipponSeiro Co., Melting point 144F (as determined from 115 K2521) In order tofind their compatibility, the mixtures were melted at 170C to see theirtransparency and they were further observed to see their flexibility atroom viscosity. The composition exhibits high transparency in its moltenstate and keeps flexibility similar to that of glue in its solid stateat room temperature owing to the fact that the components of thecomposition are excellently compatible with each other. The excellentcompatibility is further substantiated by the low cloud points shown inTable 5. These characteristics indicate that the hydrocarbon resinsaccording to this invention may advantageously be incorporated in hotmelt adhesives and coating materials. In other words, the low meltviscosity of the composition is conducive to increasing the fluiditythereof at the time of application, and the excellent compatibility ofthe composition is of service in improving it in various propertiesnecessary for an adhesive.

What is claimed is:

l. A process for the preparation of hydrocarbon solvent-solublehydrocarbon resins, characterized by polymerizing a monomeric mixturecomprising 35 percent by weight of l,3pentadiene, 5 30 percent by weightof cyclopentene and 10 50 percent by weight 11 of diisobutylene, in thepresence of a Friedel-Crafts type acidic Jrnetalhalidecatalyst.

2 A process according to claim l, wherein the monorne'ric mixturecomprises atleast one other unsaturated not more than 20 percent byweight thereof.

3. A process according to' claim 1', wherein the Friedel-Crafts typeacidic metal halide catalyst is a-rnember selected from'the groupconsisting of fluorides, chlorides, bromides and iodideso'f aluminium,boron and 4. A process according to claim 1, wherein the Friedel-Craftstype acidic metal halide catalyst is aluminum chloride.

hydrocarbon cdpolymerizable therewith in amounts of 5

1. A PROCESS FOR THE PREPARATION OF HYDROBON SOLVENTSOLUBLE HYDROCARBONRESINS CHARACTERIZED BY POLYMERIZING A MONOMERIC MIXTURE COMPRISING35-38 PERCENT BY WEIGHT OF 1,3 PENTADIENE 5-30 PERCENTBY WEIGHT OFCYCLOPENTENE AND 10-50 PERCENT BY WEIGHT OF DIISOBUTYLENE IN THEPRESENCE OF A FRIEDEL-CRAFTS TYPE ACIDIC METAL HALIDE CATALYST.
 2. Aprocess according to claim 1, wherein the monomeric mixture comprises atleast one other unsaturated hydrocarbon copolymerizable therewith inamounts of noT more than 20 percent by weight thereof.
 3. A processaccording to claim 1, wherein the Friedel-Crafts type acidic metalhalide catalyst is a member selected from the group consisting offluorides, chlorides, bromides and iodides of aluminium, boron and iron.4. A process according to claim 1, wherein the Friedel-Crafts typeacidic metal halide catalyst is aluminum chloride.
 5. A processaccording to claim 2, wherein the other unsaturated hydrocarbon is amember selected from the group consisting of butene, pentene, hexene,butadiene, isoprene, cyclopentadiene, methylcyclopentadiene, Alpha-pinene, Beta -pinene and dipentene.
 6. A process according to claim 1,wherein the polymerization is effected at temperatures of from -20*C to100*C.
 7. A process according to claim 1, wherein the polymerization iseffected in the presence of a solvent containing aromatic hydrocarbonsin amounts of at least 50 percent by weight thereof.